Dyeing preparation and its conversion to dyestuffs



Patented Aug. 14, 1934 UNITED STATES DYEING PREPARATION AND ITS CONVER- SION T DYESTUFFS Arthur Zitscher and Wilhelm Seidenfaden, Offenbach on the Main,

Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware N0 l )rawing. Application December 4, 1931, ie'aal No. 579,115. In Germany December 9,

'7 Claims.

Our present invention relates to new dyeing preparations and their conversion to dyestufis.

These dyeing preparations contain an arylanti-diazo-sulfonate corresponding to the prob-. able general formula:

X wherein X and Y mean alkyl, alkoxy or halogen, and a combining component containing a hydroxy or an O-alkali-metal group whereof the adjacent position is capable of attaching an r aryl-azo-group.

The anti-azo-sulfonates We use in our present invention are described and claimed in our copending U. S. Patent Number 1,909,851, filed December 4, 1931 and issued on May 16, 1933 in the name of Arthur Zitscher and Wilhelm Seidenfaden.

As combining components of the aforesaid kind may be named: 2-hydroXy-naphthalene, its nuclear substitution products as, for instance,

aroylamino-hydroXy-naphthalenes, (Z-hYdlOXY naphthalene 3 carbonyl) -amino-aryls (as described in U. S. Patent No. 1,101,111 and U. S. Patent No. 1,140,747), (6-halogenor arylamino- 2 hydroxy naphthalene 3 carbonyl) aminoaryls (see German Patent No. 396,519 and British Patent No. 330,349) derivatives of 1-hydroxy-naphthalene-4-carboxylic acid (see U. S. Patent No. 1,453,660) as for instance, l-hydroxynaphthalene-4-phenyl-ketone; compounds containing an acidic methylene-group capable of being combined with diazo-compounds as for instance pyrazolones and derivatives of fi-keton-aldehyde for instance aceto-acetylamino-aryls and di-(aceto-acetyl-amino) -aryls (see U. S. Patents No. 1,594,864, No. 1,594,866, No. 1,594,867, No. 1,580,709, No. 1,634,090); dihydroxy-quinolines (see U. S. applications Serial No. 352,317 and No. 352,319, U. S. Patent No. 1,820,039; British Patent No. 332,940); (2-hydroxy-carbazole-3-carbonyl) amino aryls, (2-hydroxy benzocarbazole-3-carbonyl) amino aryls, (2-hydroxy-anthracene-3-carbonyl) -amino-aryls.

These dyeing preparations yield when applied in an alkaline medium to fibers, by steaming only, insoluble azo-dyestuffs on, the fibers.

Such applying to the fibers consists in dyeing according to the one-bath-method or in printing. The dye-bath or the printing paste or also the pulverulent dyeing preparations themselves are advantageously mixed with dyeing expedients having wetting, emulsifying or dissolving properties or also with the additional agents customary in using nitrosamine-printing-colors, as, for instance, chromate.

In order to further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees. But it may be understood that our invention is not limited to the particular products or reaction conditions mentioned therein.

\ Example 1 A printing paste which contains 19 parts of the sodium salt of 4-acetylamino- 2.5-dichloro-benzene-1-anti-azo-sulfonic acid 15 parts of (2-hydroxy-naphthalene-3-carbonyl-amino) -benzene 20 parts of caustic soda lye of 34 B.

20 partsof thiodiglycol 426 parts of water 500 parts of neutral starch tragacanth-thickening is printed on textile materials. The goods thus printed are steamed for 7 minutes in the Mather-Flatt, passed through an acid bath, soaped and rinsed.

In this manner a clear dark garnet print is obtained.

Example 2 A printing paste which contains 22.3 parts of the sodium salt of 4-benzoylamino- 2-methoxy-5-chloro-benzene-1 -anti-azo -sulfonic acid 15.0 parts of (2'-hydroxy-naphthalene-3'-carbonyl-amino) -benzene 20.0 parts of caustic soda lye of 34 B.

50.0 parts of thiodiglycol 392.0 parts of water 500.0 parts of neutral starch tragacanth-thickening is printed on textile materials. The goods thus printed are slightly dried, passed through hot drying-cylinders, steamed for 10 minutes in the Mather-Flatt, rinsed at the hot, soaped and rinsed again.

In this manner a violet print is obtained.

Example 3 A printing paste containing 28.2 parts of the sodium salt of 4-benzoylamino-2-methyl-5-methoxy-benzene-l-anti-azosulfonic acid 20.0 parts of (2'-hydroxy-naphthalene-3-carbonyl-amino) benzene 30.0 parts of caustic soda lye of 34 B.

30.0 parts of thiodiglycol 372.0 parts of water 500.0 parts of neutral starch tragacanth-thickening 20.0 parts of sodium chromate solution 1:4 is printed on textile materials, somewhat dried, steamed for 10 minutes in the Mather-Flatt, soaped and rinsed.

In this manner a violet shade is obtained.

Example 4 Example 5 25 parts of l-(2'-hydroxy-naphthalene-3'-carbonyl-amino)-2-methyl4-methoxy-benzene are milled to a homogeneous mixture with 45 parts of the sodium salt of 4-benzoyl-amino-2-chloro- 5-methoxy-benzene-1-anti-azosulfonic acid of This mixture is worked up to a printing paste with 30parts of caustic soda lye of 34 B.

30 parts of thiodiglycol 350 parts of water 500 parts of neutral starch tragacanth-thickening 20 parts of sodium chromate solution 1:4 which is printed on cotton goods in the usual manner.

A red-violet print is obtained.

Example 6 15.0 parts of l-(2' hydroxy-naphthalene-F- carbonyl-amino)-2-methoxy-benzene, 4.75 parts of 4.4-bis-(aceto-acetyl-amino)-3.3'-dimethyldiphenyl, 28.0 parts of the sodium salt of 4-benzoyl-amino 2.5 -dimethoxyel-anti-azo-sulfonic acid of 87% are milled to a homogeneous mixture which is worked up to a printing paste with 25 parts of caustic soda lye of 34 B.

20 parts of thiodiglycol 387 parts of water 500 parts of neutral starch tragacanth-thlckening 20 parts of sodium chromate solution 1:4. By printing this paste in the usual manner on cotton materials a full olive-brown print is obtained.

Example 7 Bleached cotton piece-goods are impregnated with the following solution:

15 parts of (2'-hydroxy-naphthalene-3'-carbonyl-amino) -benzene '75 parts of the sodium salt of 2.5-dimethoxy- 4- (4 -methyl-benzene-sulfony1-amin0) -benzenel-anti-azo-sulfonic acid 30 parts of tragacanth-mucilage 65:1000

33 parts of caustic soda lye of 34 B.

20 parts of Turkey red oil 815 parts of water 20 parts of sodium chromate solution 1:4.

Then the goods are dried, steamed for 5-10 minutes in the Mather-Flatt, hot rinsed and soaped shortly.

In this manner a reddish violet self-dyeing is obtained.

haye inserted the Salt of the eryl-entidiazo sulfonic acid (2-hydroxy naphthalene 3 carbonyl)- compound of- Shade 1 amino 4 benzoylamino-2.5-dirnethylbenzene.

1 amino 4 benzoylamino -2 methyl 5- meghoxy-benzene.

Amino-benzene 1 amino 2 methylbenzene.

l-emino-2.5-dimethoxybenzene.

1 amino 2 ethoxybenzene.

Violet.

Claret.

Red.

Reddish violet l amino 4 chloro- Violet.

benzene.

Do 1 amino 2 methyl- Do.

benzene.

Do 1 amino 3 nitroben- Do.

zene.

Do 1- amino naphthalene. Bluish violet.

1 amino 4 benzoyl- Amino-benzene Violet. amino 2 methoxy- B-methyl-benzene.

Do l amino 2 methoxy- Garnet.

benzene.

Do 1 amino 2 metbyl- Violet.

5-chloro-benzene l amino 4 benzoyl- Amino-benzene Garnet.

amino 5 methyl 2- chloro-benzene.

Do 1-emlno-3-methyl-4- Do.

methoxy-benzene.

l amino 4 benzoyl- 1 amino 4 methoxy- Do.

amino 2 methoxybenzene. 5-0l110l'0-b0lll8l18.

Do lamino 4 methoxy- Do.

naphthalene.

l emino 4 benzoyl- Amino-benzene Red-violet.

amino 5 methoxy- 2-chloro-benzene.

' Do l amino 2 methoxy- Do.

benzene.

l-amino-4-benzoyl- Amino-benzene Reddish blue.

amino-2.5-dimethoxybenzene.

Do 1-emino-2-methoxy- Do.

benzene.

Do l-amino-naphthelene Blue.

l-amino-4-benzoyl- Amino-benzene Do.

amino-2.5-dlethoxy benzene.

Do l-emino-Z-methoxy- Reddish blue.

benzene. l-amino-4-(4'-methyll-amino-nephthelene... Violet.

benzene-V-sulionylamino) 2.5 dimeth oxy-benzene.

Do 2-nmino-nephthelene. Reddish violet.

Salt of the aryl-antldluzo sultonic acid o( Awmmpmmd Shad lnmlno-4-benzoyll-(2-hydroxy-cerbo- Brown.

mnlno-dmethoxy-Z- zole-3-carbonylcliloro-benzene. amino)-4-cl1lorobenzone.

Do 4.4-(bis-ncotoncetyl- Reddish yellow.

amino)-3.3'-dlmetliyldipllenyl.

l-om lno-4-benzoyl- 2-hydroxynopbthelene. Reddlsh violet.

emulo-2.5-dlmetboxybenzene.

Do lbydroxy-S-benzoyl- Blulsh violet.

amino-1mpl1thnlcne.

Do l-hydroxy-nnphthyl-i- Violet.

p \enyl-ketone.

Do l-phonyl-ii-methyl-G- Orange-brown.

pyrazolone.

Do 4.-l-(bls-ncetoecetyl- Gold-orange.

emlnmeedimethyldlphenyl.

Do (6'-bromo-2-hydroxy- Reddish blue.

nnphtlmlene-3-csrbony1-umlno)-benzene.

Do l-(2'-liydroxy-entbm- Bluish green.

cone-3' -carbonylemino)-2-methylbenzene.

1-emlno-4-benzoyldo Do.

amino-2.6-diethoxybenzene.

Since an object of the present invention is to produce dyestufis of good fastness properties which dyestufis are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims contain no substituents as are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. substituents of this kind are the sulfonic acid, the carboxylic acid and the hydroxy group. I

We claim:

1. As new compositions of matter the dyeing preparations comprising an aryl-anti-diazo sulfonate corresponding to the probable general formula:

acyl-NH N=N S O aalkalimetal wherein X and Y mean alkyl, alkoxy or halogen, and a combining component containing a hydroxyor an O-alkali-metal-group whereof the adjacent position is capable of attaching anarylazo-group, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuffs insoluble in water and alkali.

2. As new compositions of matter the dyeing preparations comprising an aryl-anti-diazo vsulfonate corresponding to the probable general formula wherein X and Y mean alkyl, alkoxy or halogen and R a radical of the aromatic homocyclic series, and an aromatic isocyclic compound which contains a hydroxy or an O-alkali-metal-group, a free ortho-position relative to the said group capable of attaching an aryl-azo-group and which may contain as substituents aroylamino, aroyl, halogen, arylaminocarbonyl, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestuifs insoluble in water and alkali.

3. As new compositions of matter the dyeing preparations comprising an aryl-anti-diazo sulfonate corresponding to the probable general formula:

wherein the benzene nucleus I may contain alkyl, alkoxy or halogen and Y means alkyl, alkoxy or halogen, and an aromatic isocyclic compound wherein the benzene nucleus I may contain alkyl, alkoxy, or halogen and Y means alkyl, alkoxy or halogen, and a (2-hydroxy-naphthalene-3-carbonyl) -amin0-aryl of the formula:

N=N S Graham-metal wherein Z means a radical of the benzene or naphthalene series, which dyeing preparations yield in the presence of caustic alkali by steaming azo-dyestufis insoluble in water and alkali.

5. As a new composition of matter the dyeing preparation consisting of 36.0 parts of the sodium salt of 4-benzoylamino 2-chloro-5-methoxy-benzene-1 anti diazo sulfonic acid 25.0 parts of 1-(2-hydroxyl-naphthalene-3'- corbonyl) -amino-2-methyl-4-methoxy benzene, which dyeing preparation yields when brought onto fibers by steaming red-violet dyeings and printings.

6. As a new composition of matter the dyeing preparation consisting of 52.4 parts of the sodium salt of 4-benzoylamino- 2.5-dimethoxy-benzene 1 anti-diazo sulfonic acid 37.6 parts of 1-(2'-hydroxy-naphthalene-3'- carbonyl) -2-methyl-benzene 10.0 parts of sodium hydroxide, which dyeing preparation yields when brought onto fibers by steaming reddish blue dyeings and printings.

7. As a new composition of matter the dyeing preparation consisting of 57.5 parts of the sodium salt of 4-benzoylamino-2.5-diethoxy-benzene 1 anti-diazo-sulfonic acid.

42.5 parts of the disodium salt of (2'-hydroxynaphthalene-3'-carbonyl) -amino-benzene, which dyeing preparation yields when brought onto fibers by steaming blue dyeings and printings.

ARTHUR ZITSCHER. WILHELM SEIDENFADEN. 

